Contrary to the OP's experience and other answer it seems \b is supported on Ubuntu 14.04, bash 4.3.11 as word boundary. Here is a sample:
re='\bb[0-9]+\b'
[[ 'b123' =~ $re ]] && echo "matched" || echo "nope"
matched
[[ 'b123_' =~ $re ]] && echo "matched" || echo "nope"
nope
Even \< and \> also work fine as word boundaries:
re='\<b[0-9]+\>'
[[ 'b123' =~ $re ]] && echo "matched" || echo "nope"
matched
[[ 'b123_' =~ $re ]] && echo "matched" || echo "nope"
nope
However support of \b is specific to certain OS only. e.g. on OSX following works as word boundary:
[[ 'b123' =~ [[:\<:]]b[0-9]+[[:\>:]] ]] && echo "matched" || echo "nope"
matched
[[ 'b123_' =~ [[:\<:]]b[0-9]+[[:\>:]] ]] && echo "matched" || echo "nope"
nope